Coloring matter derived from pyrazolones



Patented pa. 4,1934

UNITED STATES" COLORING MATTER DERIVED FROM A PYRAZOLONES Ralph B. Payne, Elma, and Karl Friedrich Conrad, Bufl'alo, N. Y., assignors to National Aniline and Chemical Company, Inc., New York, N. Y., a corporation of New York no Drawing.

Application May 26, 1930,

Serial No.. 455,947

20 Claims.

The present invention relates to new coloring matters and to compositions containing the same.

The process of preparing the new coloring matters and the process of preparing the compositions containing the same also form a part of the present invention.

The new coloring matters of the present invention comprise the organic reaction products of a dyestufi containing an acid group in its molecule 10 with a pyrazolone compound. Further, in accordance with the present invention, the new coloring matters may be compounded with plastic, coating or molding compositions, such as natural or artificial resins (e. g., shellac, Bakelite resins,

i5 urea-formaldehyde resins, etc.) pyroxylin, cellulose esters and ethers, varnish, etc., with or without the presence 01' a suitable solvent therefor,

they may be employed in the preparation of pigments or lakes, or they may be employed in solution with a suitable solvent as stains, etc.

In accordance with the present invention, the new coloring matters may. be prepared by reacting a pyrazolone compound with a dyestufl containing at least one acid group, particularly a sulfonic group, in its molecule. The combination conveniently may be effected by reacting, in the presence of an acid or of an alkali, a metal salt of the said dyestufi with a pyrazolone. The reaction is preferably carried out in an aqueous medium by adding to a hot water solution of the water soluble metal salt or the dyestufi a solution oi a pyrazolone compound in dilute acid to form the new coloring matter which is precipitated out of solution, and may be separated, as by filtration,

and dried.

In general, the new coloring matters differ in solubility in various solvents in a marked degree from the parent dyestuffs from which they are prepared. Their solubility in various solvents, as

well as other properties, depend on whether the combination is efiected in acidor alkaline medium. Generally, the solubility in water of the new coloring matters is less than'that oi the par ent dyestufls. Those which are insoluble in water are useful as pigments, lakes, etc., while those which are soluble in alcohol, or in ethyl acetate, amyl acetate, acetone, etc., are useful in lacquers, stains, etc. The shade or color of the new coloring matters may or may not be different irom 60 that of the initial dye.

The new coloring matters may be incorporated with various compositions, as hereinbeiore mentioned. varnishes colored with the new spirit soluble coloring matters furnish coatings dis-' tinguished by richness of shade and brightness on materials of all kinds. The alcohol soluble new coloring matters further have a distinct advantage over oil soluble dyes ordinarily used in celluloid compositions in that celluloid plastics colored with the new dyes can be cemented to white or to other different shades of celluloid without bleeding. The new alcohol soluble dyes are particularly desirable for staining wood which is to be coated with a pyroxylin lacquer, since no running of the color occurs.

The above general designation a dyestufl containing at least one acid group in its molecule will readily be understood to denote and include dyestufis of all classes, or salts thereof, which contain true acid groups, such as the sulfonic acid group or carboxylic acid group, and particularly those of the class of acid dyestuffs, and not to include dyestuffs which contain a phenolic hydroxyl group but not a true acid group. The invention is particularly applicable to the conversion into new coloring matters of acid dyestuffs of the azo class, such as the monazo-, disazo-, trisazo-, etc., acid dyes, and more particularly of the monazo dyestuiis containing a sulfonic group. Among the large number of dyestuffs which may 80, be converted into the new dyestuffs of the present invention may be mentioned the following:

Colour Index Wool Orange AZ 151 Alphazurine 1 G 671 Alizarine Cyanine Green GX 1078 Fast Wool Yellow 3GL m 636 Crocein Scarlet MOO 252 Crocein Orange Y 26 Lake Scarlet R '19 Metanil Yellow 138 Wool Orange 2G 27 Azornhino 179 Fast Crimson GR 31 Fast Crimson GBL 5'? W001 Orange R 161 Fast W001 Blue R 208 Rhodamine 749 The term pyrazolone compound, as used in the specification and claims, will be understood ,to denote and include pyrazolone and substituted pyrazolones, for example, pyrazolone carboxylic acid, aryl pyrazolones, aryl' pyrazolone carboxylic acids, aryl-alkyl-pyrazolone-carboxylic acids, and

aryl-alkyl-pyrazolones which may also contain alkyl groups and/ or inorganic substituents in the aryl nucleus, more particularly the phenylmethyl-pyrazolones. The pyrazolone compounds of the 5-py razo1one series are especially of value.

Examples of suitable compounds are antipyrene, 1-phenyl-3-methyl-5-pyrazolone, l-(p-sulfophenyl) -3 methyl 5-pyrazolone, 1 -(2 chlor 5'- sulfophenyl) -3-methyl-5-pyrazolone, 1-phenyl-3- carboxy-5-pyrazolone, 1-phenyl-3-pyrazolone, 1- phenyl-5-methyl-3-pyrazolone, etc.

- We are unable to definitely state the nature or composition of the new organic coloring matters, although we believe that they are probably addition compounds of the pyrazolone compounds with the dyestufis employed. Due to the amphoteric nature of the pyrazolones, particularly the phenyl methyl pyrazolones, two series of the new coloring matters may be formed, one series by reaction in the presence of an alkali, and the other series in the presence of an acid. The reaction between the pyrazolone compounds and the acid dyestuffs is not a coupling reaction of a diazo compound with a pyrazolone compound, and it is to be understood that such coupling reactions are not included within the scope of the present invention.

The invention may be illustrated by the following examples: The parts are by weight.

Example 1.To a boiling solution of 50 parts of the sodium salt of 4-benzene-azo-1-(2-chlor- 5'-sulfophenyl) -3-methyl-5-hydroxypyrazol dissolved in 2000 parts of water, there is added an aqueous solution containing about 2.6 per cent. of 1-phenyl-3-methyl-5-pyrazolone and 3.4 per cent. of hydrochloric acid until the precipitation of the new coloring matter is substantially complete. The precipitated coloring matter is filtered hot, washed and dried. It is a yellow powder sparingly soluble in water, soluble in alcohol, acetone, amyl acetate and ethyl acetate.

Example 2.To a boiling solution of 10 parts Fast Wool Yellow SGL in the form. of the mono sodium salt, dissolved in 500 parts of water, there is added an aqueous solution containing about 8.6 per cent. of antipyrene and 5.3 per cent. of 1101 until the precipitation of the new coloring matter is substantially complete. The precipitated coloring matter is filtered ofi, washed and dried. It is a yellow powder, sparingly soluble in water and soluble in alcohol.

Example 3.-To a boiling solution of 10 parts Alphazurine FG in the form of the ammonium salt, dissolved in 500 parts of water heated to boiling, there is added an aqueous solution containing about 8.6 per cent. phenyl methyl pyrazolone and 5.3 per cent. HCL, until the precipitation of the new coloring matter is substantially complete. The precipitated coloring matter is filtered, washed and dried. It is a blue powder, sparingly soluble in water and soluble in alcohol.

Example 4.-By following the procedure described in Example 3, using 10 parts Alizarine Cyanine Green GX as its sodiinn salt in place of the Alphazurine FG, a new coloring matter is obtained, which when dried and powdered, is a green powder, soluble in alcohol.

Example 5.By following, the procedure described in Example 3, using 10 parts wool orange A as its sodium salt, in place of Alphazurine FG, a new coloring matter is obtained, which, when dried and powdered, is an orange powder soluble in alcohol.

The procedure, as described in the above examples, is not dependent upon any theory for its operativeness, it being only necessary to add the acid solution of the pyrazolone compound until reaction is complete, as indicated when no increase in the quantity of precipitate is noted. The proportion of water and acid employed, the

a pyroxylin lacquer prepared by mixing.

temperature, and other conditions may be varied through wide limits. Also in place of hydrochloric acid, other mineral acids, e. g., sulfuric acid, or organic acids, e. g., acetic acid, may be employed.

Example 6.To a boiling solution of 25 parts Crocein Orange Y in the form of the mono sodium salt dissolved in 1500 parts of water, there is added an aqueous solution containing about 25 parts 1-phenyl-3-methyl-5-pyrazolone and 10 parts soda ash in 500 parts water. The precipitated coloring matter is filtered off, washed and dried. It is an orange powder, sparingly soluble in water and insoluble in alcohol.

In a similar manner, the alkaline series of new coloring matters may be produced by dissolving a pyrazolone compound in a suitable alkali, for example, caustic soda, soda ash, etc., and adding the resulting solution to a solution of the dyestuif. The precipitate which forms is washed and dried in a similar manner.

Example 7.-Pyro:cylin molding composition One part yellow coloring matter, obtained by reacting in acid solution the sodium salt of 4- benzene-azo 1 -(2- chlor 5'- sulfophenyl) 3 methyl-5-hydroxypyrazol with phenyl methyl pyrazolone as described above in Example 1, is dissolved in 1 gallon alcohol, and suflicient of this solution is then added to a mixture of Parts Pyroxylin 100 Camphor 35 Urea l to produce the desired shade. This colored plastic mass is then molded under heat and pressure.

Example 8.--Wood stain Example 9.Pyromylin lacquer One ounce blue coloring matter, obtained by reacting in acid solution Alphazurine FG with phenyl methyl pyrazolone, as described above in Example 3, is dissolved in one pint of denatured alcohol. 'Sufllcient of this solution is added to to produce the desired shade.

Example 10.--"Balcelite C composition Parts 100 Bakelite A Wood flour 100 Orange coloring matter (prepared as described in Example 5) 2 The above ingredients are intimately mixed and then milled into sheets, powdered, and molded under heat and pressure to form a colored "Bakelite C composition.

Since changes in the invention above described may be made without departing from its scope. the above description is to be construed as illustrating rather than limiting the invention. It is also to be understood that the following claims are intended to cover the generic and specific features of the invention herein disclosed, and all statements of thescope of the invention which, as a matter of language, might be said to fall therebetween.

We claim: A.

1. A composition of matter comprising the organic reaction product of a pyrazolone compound with a dyestufl! containing at least one acid group but not containing a diazo group.

2. A composition of matter comprising the organic reaction product of an aryl pyrazolone compound with a-dyestufi containing at least one acid group but not containing a diazo group.

3. A composition of matter comprising the organic reaction product of a pyrazolone compound in acid solution with a salt of an acid dyestufl which does not contain a diazo group.

- pound with an azo dyestufi containing at least one acid group but not containing a diazo group.

5. A composition of matter comprising the organic reaction product of an aryl-5-pyrazolone compound with a dyestui! containing at least one acid group but not containing a diazo group.

6. A composition of matter comprising the organic reaction product of a phenyl methyl-pyrazclone with an azo dyestufi containing at least one acid group but not containing a diazo group.

7. A composition of matter comprising the organic reaction product of 1-phenyl-3-methylfi-pyrazolone in acid solution with a soluble metal salt of a monazo dyestufl containing at least one sulio group but not containing'a diazo group.

8. A composition of matter comprising the organic reaction product of 1-phenyl-3-methyl-5- position which comprises reacting a pyrazolone compound in acid solution with the soluble metal salt of an azo dyestufl containing at least one acid group but not containing a diazo group. 13. The process for producing a colored composition which comprises reacting an aryl pyrazclone in acid solution with a soluble metal salt of a dyestuflf containing at least one acid group but not containing a diazo group.

14. The process for producing a colored composition which comprises reacting an aryl-fi-pyrazolone compound in acid solution with a soluble metal salt of an azo dyestufi containing at least one acid group but not containing a diazo group.

15. The process for producing a colored composition which comprises reacting a phenyl methyl pyrazolone compoundwith an azo dyestufl containing at least one acid group but not containing a diazo group.

16. The process for producing a colored composition which comprises reacting1-phenyl-3- methyl-5-pyrazolone in acid solution with a soluble metal salt of a monazo dyestuil' containing at least one sulio group but not containing a diazo group.

17. The process for producing a colored composition which comprises reacting 1-phenyl-3- methyl-5-pyrazolone in acid solution with the sodium salt oi 4-benzene-azo-1-(2'-chlor-5-sultophenyl) -3-methyl-5-hydromyrazol.

18. The process for producing a colored composition which comprises reacting 1-phenyl-3- methyl-S-pyrazolone in acid solution with wool orange A in the form of an alkali metal salt.

19. A composition of matter comprising the organic reaction product of 1-phenyl-3-methyl-5- pyrazolone in acid solution with Crocein Scarlet MOO.

20. The process for producing a colored composition which comprises reacting 1-phenyl-3- methyl-S-pyrazolone in acid solution with Crocein Scarlet Mp0.

. RALPH B. PAYNE.

KARL FRIEDRICH CONRAD. 

